A photographic composition of 1,1-bis-sulfonyl alkane and hydroxylamine

ABSTRACT

A combination of 1,1-bis-sulfonyl alkane silver halide solubilizing agent with a hydroxylamine silver halide developing agent in a photographic chemical transfer process, element, composition and/or product provides a developed image having increased stability, with low minimum density, increased maximum density and desired sensitometric properties. This combination can include addenda commonly employed in photographic processing compositions and elements.

United States Patent 1 Yungkurth et a].

[ Nov. 6, 1973 A PHOTOGRAPHIC COMPOSITION OF 1,1-BIS-SULFONYL ALKANE ANDHYDROXYLAMINE [75] Inventors: Donald G. Yungkurth; Gary J.

McSweeney, both of Rochester, NY.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

[22] Filed: Oct. 1, 1971 21 Appl.No.: 185,830

[52] US. Cl...'. 96/29 R, 96/94, 96/109 [51] Int. Cl G03c 5/54 [58]Field of Search 95/109, 29

[56] References Cited UNITED STATES PATENTS 3,647,453 7 3/1972 Haist etal 96/109 3,293,034 12/1916 Green et al. 96/61 X Primary ExaminerNormanG, Torchin Assistant Examiner-John L. Goodrow AttorneyRobert W. Hamptonet al.

[ ABSTRACT 13 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Fieldof'the Invention This invention relates to photographic processingcompositions, elements and processes. In one of its aspects it relatesto photographicprocessing compositions containing a combination of'ral,l-bis-sulfonyl alemulsion layer; After exposure of the photographiclayer, a processing composition is applied between the exposedphotographic layer and the silver precipitating layer. The processingcomposition usually contains a silver halide solvent which causes theunexposed silver salts, usually silver halides, to form a silver complexwhich diffuses to the image receiver or silver precipitatin g. layerwhere development nuclei or precipitating agent'within that layer causesthe silver to be precipitated from the silver complex. Developmentnuclei can be present in the image receiving layerbefore contact withthe complex or the nuclei can be formed in situ. Diffusion transferphotographic systems are described, for example, in US. Pat. No.2,698,237 of Land issued Dec. 28, 1954; U.S. Pat. 'No. 2,647,056 ofLandissued July'28, 1953; U.-S.'Pat; No. 3,108,001 ofGreen issued Oct. 22,1963; and U.S. Pat. No. 3,345,166 of Land issued Oct. 3,. 1967.-The'processing composition employed in a chemicaltransfer systemnormally contains a silver halide solubilizing agent and a silver halidedeveloping agent'and' is usually applied as-a viscous fluid layer spreadbetween the photosensitive layer and the image receiving layer.

Likewise, silver halide complexing agents have been employed inmonobaths wherein a single processing composition can be utilized toboth develop and fix or stabilize a photographic silver halide emulsionlayer.

Such compositions contain a silver halide developing agent in additionto the silver halide solubilizing agent.

Many compounds have been tried as silver halide solubilizing orcomplexing agent in the described systems. One commonly employed silverhalide solubilizing or complexing agent employed is sodium-thiosulfatepentahydrate. Other silver halide solubilizing or complexing agentswhich have been employed include potassium thiocyanate and certainmercaptans such as mercapto acetic acid. These and other silver halidesolubilizing or fixing agents have not been found satisfactory whenemployed with hydroxylamine silver halide developing agents due to theproduction of undesired maximum and minimum density in the developedimage. This is illustrated in the following comparative exampies, 2, 3,4, 5 and 6.

2 The requirements for developing agents to be employed with thedescribed silver halide complexing agents in a chemical transfer systemto provide the desired stable image are very stringent and relativelyfew of the developing agents which are satisfactory for general silverhalide developing systems will be satisfactory I or sufficiently activefor chemical transfer systems.

Commonly employed developing agents include hydroqu'inone, pyrocatechol,araboascorbic acid, or a reductone developing agent such as dihydroanhydro piperidino hexose reductone. Although such developing agentswill produce a positive image in a chemical transfer system whenemployedwith certain silver halide complexing agents, they provide less thandesired maximum and minimum densities. This is illustrated in thefollowing comparative Examples 7 and 8. I

Thus, there has been a continuing need for a combination of a silverhalide complexingagent with a silver halide developing agent whichprovides improved maximum and minimum densities and developing actionwith improved developed image stability and without objectionable stainon a processed print.

SUMMARY OF THE INVENTION According to the invention it has been foundthat desired increased maximum and minimum density without undesiredoxidation stain, and with improved developed image stability can beprovided in a chemical transfer-system employing a combination of .a l,l-bissulfonyl alkane silver halide solubilizing agent with ahydroxylamine silver halide developing agent.

This combination of silver halide complexing agent with a hydroxylaminesilver halide developing agent provides excellent silver halidesolubilizing or fixing properties and developing properties in a rangeof photographic processes and products wherein silver halide solventsand developing agents are ordinarily employed in combination. Thiscombination can be employed with an auxiliary silver halidedevelopingagent DETAILED DESCRIPTION OF THE INVENTION A range of the describedl,l-biss ulfonyl alkanes, also known as beta-disulfones, can be employedin combination with a hydroxylamine silver halide developing agentaccording to the invention. The betadisulfones and their chemicalreactions have been described in the literature. For example, thepreparation of these compounds and reactions in which they are involvedare described in Suter, ORGANIC CHEMIS- TRY OF SULFUR, pages 735 and739. Of the class of beta-disulfone compounds, however, it has beenfound that particular beta-disulfones, such. as l,l-bis-sulfonyl alkanesare excellent silver halide solvents with hydroxylamine silver halide.developing agents. Suitable 1,1- bis-sulfonyl alkanes employed accordingto the invention can be represented by the formula wherein R and R eachrepresent an alkyl group containing one to four, carbon atoms and Rrepresents hydrogen or an'alkyl group containing one to four carbonatoms. The term alkyl as employed herein also includes substituted alkylgroups and preferably substituted lower alkyl group containing from oneto four carbon atoms. Substituted alkyl groups include hydroxyalkylgroups, e.g., hydroxyethyl or hydroxybutyl; alkoxyalkyl group such asmethoxyethyl or butoxybutyl; carboxyalkyl such as a carboxyethyl orcarboxybutyl; sulfoalkyl such as a sulfoethyl or sulfobutyl;sulfatoalkyl such as a sulfatoethyl or sulfatobutyl; an acyloxyalkylsuch as beta-acetoxyethyl or butyloxybutyl; or alkoxycarbonylalkyl suchas a beta-methoxycarbonylethyl or ethoxycarbonylbutyl.

1,1-Bis-sulfonyl alkanes within the described formula include, forexample, l,l-bis-(methylsulfonyl)ethane; 1 ,1-bis-(ethylsulfonyl)ethane; l ,1 -bis-(methylsulfonyl )-propane; 1-ethylsulfonyll methylsulfonylmethane; l-ethylsulfonyll-methylsulfonylethane and the like. Especially useful 1,1-bissulfonylalkanes are bis(methylsulfonyl)methane, bis (ethysulfonyl)methane,bis(beta-hydroxyethylsulfonyl )methane, bis-(carboxymethylsulfonyl)methane, and bis(beta-carboxyethyl-sulfonyl)-methane.

A range of hydroxylamine silver halide developing agents can be employedin the described combination also. Useful hydroxylamine silver halidedeveloping agents include, for example, compounds of the forwherein R,and R are each, individually, hydrogen, alkyl containing one to fourcarbon atoms, alkoxyalkyl containing three to six carbon atoms, oralkoxyalkoxyalkyl containing five to carbon atoms. Typical hydroxylaminesilver halide developing agents within this formula includehydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine,N-propylhydroxylamine, N-isopropylhydroxylamine,N,N-diethylhydroxylamine, N,N-dimethylhydroxylamine, N-methyl-N-propylhydroxylamine, N-methyl-N-isopropylhydroxylamine, N-ethyl-N-ripropylhydroxylamine, N,N-diisopropylhydroxylarnine,N,N-di-n-propylhydroxylamine, N-ethyl-N-methylbutylhydroxylamine,N-methyl-N-isobutylhydroxylamine, N-ethyl-N- hydroxyethylhydroxylam'ine,N-hydroxyethyl-N- carboxyethylhydroxylamine, N,N-di- (methoxyethyl)-hydroxylamine, N,N-di( 2- ethoxyethyl)hydroxylamine,N,N-di-(2-methoxyethoxyethyl)hydroxylamine, and the like. Hydroxylaminesilver halide developing agents are set out, for example, in U.S. Pat.No. 2,857,276 of Land et al., issued Oct. 21, 1958; U.S. Pat. No.2,857,275 of Land et al., issued Oct. 21, 1958 and U.S. Pat. No.2,857,274 of Land et al., issued Oct. 21, 1958, as well as a NetherlandsPat. No. 7015734 of Gevaert- Agfa; U.S. Pat. No. 3,343,958 of Morse,issued Sept. 26, 1967; British Pat. No. 902,314 of Polaroid, pubet al.,issued Nov. 22, 1966; U.S. Pat. No. 3,287,125 of Green et al., issuedNov. 22, 1966; U.S. Pat. No. 3,293,034 of Green et al., issued Dec. 20,1966; U.S. Pat. No. 3,362,961 of Green et al., issued Jan. 9, 1968;British Pat; No. 1,142,134 of Polaroid, published Feb. 5, 1969;U;S.-Pat. No. 3,455,916 ofGreen et al., issued July [5, 1969; U.S. Pat.No. 3,467,711 of Bader et al., issued Sept. 16, 1969 and the like.

One embodiment of the invention is accordingly a photographic processingcomposition comprising a 1,1- bis-sulfonyl alkane silver halidesolubilizing agent with a hydroxylamine silver halide developing agent,as described. Such a processing composition is typically an aqueousalkaline processing composition.

Various development activators can be employed in combination with thedescribed beta-disulfone silver halide solubilizing agent andhydroxylamine silver halide developing agent. These include any of thosewhich provide the desired activation of the described developing agentsand desired silver halide solvent activity. These include, for example,alkaline development activators, such as inorganic alkalies including,for example, sodium hydroxide, potassium hydroxide,

cesium hydroxide and/or lithium hydroxide; alkali metal carbonates, suchas sodium carbonate, and potassium carbonate; alkali metal phosphates,such as tri-.

sodium phosphate and/or organic alkaline development activators, such asquaternary ammonium bases and salt, such as amino alkanols and similaralkaline materials and/or alkali releasing materials. In some instancesthe described hydroxylamine silver halide developing agent is alkalineand contributes to the alkalinity of the processing composition.

The described silver halide solubilizing agents can be utilized in aphotographic processing composition in a concentration of at least about1 gram of disulfone per liter of processing composition. Theconcentration of such silver halide solubilizing agents can vary over awide range depending on the particular components of the processingcomposition, the desired image, the particular photographic silverhalide emulsion employed, processing conditions and the like. Generally,however, the concentration of described disulfone utilized will varybetween about 0.1 and about 1.0 moles of the described l,l-bis-sulfonylalkane silver halide solubilizing agent per liter of processingcomposition.

When the described disulfones are employed in processing compositionsfor clearing or fixing silver halide in developed photographic elements,usually at least about 5 to' 200 grams of the beta-disulfone is employedper liter of processing composition to obtain the fixing within apractical time. Lower concentrations can be employed when the describeddisulfone is employed as a silver halide solubilizing agent in a silversalt chemical transfer system.

The described disulfone siiver halide complexing agents provide fixingor clearing action in alkaline or basic compositions. Generally alkalinecompositions have a pH of at least 8 or 9, and preferably at least about1 l, are employed. However, the alkalinity of the processingcompositions can vary over a wide range de pending upon the particularphotographic element processed, particular processing condition, thehydroxylamine silver halide developing agent employed, processing timeand the like.

A range of concentration of the described hydroxylamine silver halidedeveloping agent can be employed in the combination according to theinvention. A suitable concentration is typically about 0.10 mole toabout 1.50 mole of hydroxylamine silver halide developing agent perliter of processing composition.

An especially useful processing composition is an aqueous alkalinephotographic processing solution containing bis(methylsulfonyl)methanewith N,N-diethylhydroxylamine.

While it is especially useful in a chemical transfer system to employthe described combination of disulfone silver halide solubilizing agentand hydroxylamine silver halide developing agent in a processingcomposition, such as an aqueous alkaline processing solution, thedescribed combination can be employed'in the practice of the inventionin a range of physical locations in av photographic chemical transfersystem. For

instance, the disulfone silver halide solubilizing agent can be employedin one ormore layers of aphotographic element and/or in a processingcomposition, if desired. The optimum location will depend upon thedesired image, processing conditions, particular photographic system andthe like. An especially useful locaa wide range depending, primarily,upon the concentration of silver halide present initially inthe'photosensh tive element and the degree it is desired to dissolve orsolubilize'the silver halide; The fact that the described disulfones canbe incorporated in a photosensitive element is an importantcharacteristic of these compounds. Silver halide solubilizing agentcommonly employed, such as sodium thiosulfate pentahydrate, cannot besuccessfully incorporated in a photographicelement,,especially in'aphotographic silver halide emulsion layer since it provides undesiredsilver halide solvent action upon contact with the silver halide. Thedescribed disulfones, on the other hand, are relatively inert at a pHrange below about 8 or 9 and, therefore, can be coated as a component ofa photographic element at the pH or below. The disulfones become activesilver halide solvents above this pH range. Alkaline activation of thedescribed disulfone silver halide solubilizing agents with thehydroxylamine silver halide developing agents thus can provide bothsilver halide developing activity and silver halide solvent activity.

Another embodiment of the invention accordingly is a photographicelement comprising a support, photographic silver halide, a1,1-bis-sulfonyl alkane silver halide solubilizing agent with ahydroxylamine silver halide developing agent. A typical photographicelement comprises a support, photogrpahic silver halide,bis(methylsulfonyl)methane with N',N-diethylhydroxylamine.

When employed in a photographic element, a concentration of thedescribed disulfone can vary dependprocessing condition and the like butis typically about 0.24 mole to about 4 moles of the described disulfoneper mole of silver halide present in the photographic element. Asuitable range of hydroxylamine silver halide developing agent in aphotographic element with the disulfone can also vary depending upon thedeing upon the components of the photographic element, 5

posed photographicsilver halide by contacting the element with analkaline photographic processing composition containing a silver halidesolubilizing agent with a silver halide developing agent, theimprovement which comprises employing a 1,1-bis-sulfonyl alkane as thesilver halide solubilizing agent with a hydroxylamine developing agentas the silver halide developing agent. This photographic elementcanprovide a means for rapid access processing. 4

If desired, an alkaline solution containing conventional silver halidedeveloping agents can be employed for activating the describedhydroxylamine silver halide developing agent when employed in aphotographic element. So-called web processing can be employed, asdescribed, for example, in US. Pat. No. 3,179,517 of Tregillus et alissued Apr. 20, 1965 or so-called stabiliz a tio n processing asdescribed in Russell et al., PSA

Journal, Volume 1613, Aug, 1950.

The time for. processinga photographic element in .20

the practice of the invention which includes developing a desired latentimage can vary over a wide range typically between about 1 second toseveral minutes depending-on the processing conditions, particulardeveloping agents, particular silver halide solubilizing agent,

desired image and the like.

The conditionsfor processing can also vary, but usually ambientpressures and temperatures-of about 10C.

to about 40C. are employed.

The described combinationof disulfones with hydroxylamine silver halidedeveloping agents aredesirably employed in photographic chemicaltransfer systems, especially photographic silver s'alt chemicalvtransfer systems. The described combination can be employed individuallyor in combination in one or more layers of photographic elementand/or ina processing composition in ,such a system if desired. Suitable chemicaltransfer systems, processes, processing compositions and elementstherefor are described, for example, in 11.8. Pat. No. -2,452,l8l ofLand issued Feb. 27, 1951; US. Pat. No. 3,337,342 ofGreen issued Aug.27, 1967, the disclosures of which are incorporated herein by reference.They can be used in socalled high speed diffusion transfersystems,processes and compositions therefor as described, for example, in 11.8.Pat. No. 3,326,683 'of-Land et al. issued June 20, 1967; or in othertypes of chemical transfer systems such as described in US. Pat. No.3,020,155 of Yackel issued Feb. 6, 1962; US. Pat. No. 2,584,030 of Landissued Jan. 29, 1952 and Belgian Pat. Nos. 749,931; 749,932; 749,933;749,934; 749,935; and 749,930 published Oct. 16, 1970. These referencesare incorporated herein by reference and describe typical photoscribedfactors but is typically about 0.24 moles to about 4 moles ofhydroxylamine silver halide developing agent per mole of silver halidein the photographic element. The concentration of the disulfone andhydroxylamine silver halide developing agent which is most suitable willdepend on the location in the photographic element, the concentration ofsilver'halide to be dissolved and the like.

Accordingly, another embodiment of the invention is I in a process fordeveloping and stabilizing an image in a photographic element comprisinga support and exgraphicproducts suitable for diffusion transfer systemscomprising in combination (a) a photographic element comprisingphotographic silver halide, (b) a processing composition containing asilver halidesolvent, typically in a rupturable container, and (c) animage receiving layer. Accordingly another embodiment of the. inventionis: in a photographic diffusion transfer product comprising incombination (a) a photographic element comprising photographic silverhalide, (b) a processing composition comprising a silver halidesolubilizing agent and (c) an image receiving layer, the productcontaining a silver halide developing agent, the iniprovement comprisinga combination of 1,1-bis-s ulfony alkane as the silver halidesolubilizing agent and a hydroxylamine silver halide developing'agent asthe described developing agent. The described combination of silverhalide solubilizing agent and silver halide developing agent ispreferably present in the processing composition.

The described combination of disulfone with hydroxylamine silver halidedeveloping agent can be employed in a photographic silver salt diffusiontransfer process comprising developing a latent image in a photographicdiffusion transfer product comprising (a) a photographic elementcomprising photographic silver halide, (b) a processing compositioncomprising a silver halide solvent, and (c) an image receiving layerwherein the l,l-bis sulfonyl alkane as described is em ployed as thesilver halide solubilizing agent and a hydroxylamine is employed as thesilver halide developing agent. More particularly this process can, forexample, comprise the steps of exposing a photographic silver halidelayer to form a latent image therein; developing the latent image with aprocessing composition, such as at a pH of about 12 to about 14,comprising the described hydroxylamine silver halide developing agent;

contacting undeveloped silver halide in the photo-' graphic silverhalide layer with a l,l-bis sulfonyl alkane silver halide solvent toform an imagewise distribution of a silver complex in the unexposedareas of the photographic silver halide layer; transferring at least.part of the silver complex to an image receiver layer contiguous to thephotographic silver halide layer; reducing the silver complex in thepresence of development nuclei to form a visible image in the receiverlayer; and then, typically, lowering the pH of the processingcomposition to about 8 or below to form a stable developed image on theimage receiver.

A wide variety of development nuclei or silver precipitating agents canbe employed in diffusion transfer systems as described. These can bephysical development nuclei or chemical precipitants including, forexample, heavy metal in colloidal form and salts of these metals, saltsof amines which form silversalts and/or non-diffusing polymericmaterials with functional groups capable of combining with silveramines.

Suitable development nuclei and/or silver image precipitating agentswithin the described classes include metal sulfides,-sulfonides,plysulfides, polyselenides, thiourea and its derivatives; stannoushalides, sulfur, gold, platinum, palladium and mercury, colloidal silversulfur, aminoguanidine sulfate, aminoguanidine carbonate, arsenousoxide, sodium stannate, hydrazines, xanthates and similar agentsdisclosed, for example, in U.S. Pat. No. 3,020,155 of Ya'ckel et al.issued Feb. 6, 1962. A typical non-diffusing polymeric silverprecipitant is poly (vinylmercaptoacetate). A range of concentration ofdevelopment nuclei or silver precipitating agent can be employed. Aconcentration of the development nuclei or silver precipitant in theimagereceiving layer must be at least sufficient to insure thedevelopment of a positive image and sufficient removal of undevelopedsilver salt from the light sensitive layer to be processed.

The described silver precipitating agents or development nuclei canbeutilized in image reception layers that are separate elements from thelight sensitive silver halide element processed or they can be utilizedas reception layers integral with the light sensitive element. When thereception layer is integral with the light sensitive element, thereception layer is generally a sublayer over which is coated the silverhalide in a vehicle that is readily removable during processing, such asa hydrophilic colloid soluble in aqueous alkali such as cellulose etherphthalate.

Due to the inertness of the described disulfones, they can beincorporated in a receiving layer for chemical transfer systems. Again,the concentration of the disulfone can vary over a wide range dependingon the concentration of the silver halide present in the system to bedissolved. The concentration can be about 0.25 to about 4 moles ofdescribed disulfone per mole of silver halide-in the light sensitiveelement.

The described photographic element, receiving layers and/or processingcompositions can also contain toning agents. Typical toning agents whichcan be employed include, for example, polyvalent inorganic-salts asdescribed in U.S. Pat. No. 2,698,236 of Land issued Dec. 28, 1954;silica as described in U.S. Pat. No. 2,698,237 of Land issued Dec. 28,1954 and heterocyclic mercaptans such as mercaptoazoles, such asmercaptodiazoles, mercaptotriazoles, mercaptotetrazoles andcorresponding selenazoles.

A processing composition employed in a diffusion transfer system asdescribed is typically a viscous processing composition. A wide range ofviscosity can be employed The viscosity can be about 20 to about100,000centipoise typically about 100 to about 10,000 centipoise.Various thickening agents are suitable in the described processingcompositions and processes of the invention. Any of those commonlyemployed in diffusion transfer photographic systems can be employed aswell as those employed in viscous monobaths. These include thosedescribed, for example, in U.S. Pat. No. 3,120,795 of Land issued Feb.11, 1964 such as hydroryethylcellulose and carboxymethylcellulose.

The described combination of a l,l-bis-sulfonyl alkane silver halidesolubilizing agent with a hydroxylamine silver halide developing agentcan be employed in combination with silver halide developing agentswhich are not hydroxylamines. .The developing agents can be employed insuch combinations as auxiliary developing agents or as the maincomponent of a developing combination. Suitable silver halide developingagents which can be employed include, for example, polyhydroxybenzenes,such as hydroquinone silver halide developing agents, e.g.,hydroquinone, alkylsubstituted hydroquinones as exemplified by tertiarybutyl hydroquinone, methyl hydroquinone, 2,5- dimethyl hydroquinone and2,6-dimethyl hydroquinone; catechols and pyrogallols; chloro-substitutedhydroquinones, such as chlorohydroquinone or dichlorohydroquinone;alkoxy-substituted hydroquinone British Pat. No. 1,045,303 publishedOct. 12, 1966 and V the like. Combinations of these developing agentscan be employed, if desired.

Silver halide emulsions which can be employed with this invention can besilver chloride, silver bromide, silver bromoiodide, silverchlorobromoiodide or mixtures thereof. The emulsions can be coarseorfine-grain and can be prepared by any of the well-known procedures inemulsion making such as single-jet emulsions, double-jet emulsions,-such as Lippmann, ammoniacal emulsions, thiocyanate or thioetherripened emulsions, such as those described in U.S. Pat. No. 2,222,264 ofNietz et al. issued Nov. 4, 1940; U.S. Pat. No. 3,320,069 oflllingsworth issued May 15, 1967 and U.S.

Pat No. 3,271,157 of McBride issued Sept. 6, 1966.

Surface image emulsions can be used or internal image emulsions such asthose described in U.S. Pat. No. 2,592,250 of Davey et al. issued Apr.8, 1952; U.S. Pat. No. 3,206,313 of Porter et al. issued Sept. 14, 1965;U.S. Pat. No. 3,367,778 of Berriman et al. issued Feb.

6, 1968; and Belgian Pat. No. 704,255. If desired, mixtures'of surfaceand internal image emulsions can be used, as described in U.S. Pat. No.2,996,382 of Luckey et al. issued Aug. 15, 1961. Negative type emulsionscan be used or direct positive emulsions such as those described in U.S.Pat. No. 2,184,013 of Leermakers issued Dec. 19, 1939; U.S. Pat. No.2,541,472 of Kendall et al. issued Feb. 13, 1951; U.S. Pat. No.3,367,778 of Berriman et al. issued Feb. 6, 1968; British Pat. 723,019;French Pat. No. 1,520,821; U.S. Pat. No. 2,563,785 of Ives issued Aug.7, 1951; U.S. Pat. No. 2,456,953 of Knott et al. issued Dec. 21, 1958and us. Pat. No. 2,861,885 of Land issued Nov. 25, 1958. The emulsionscan be regular grain emulsions such as those described in Klein andMoisar, Journal of Photographic Science, Volume 12, No. 5,September-October, 1964, pages 242-251.

The silver halide emulsions employed in the practice of the inventioncan be unwashed or washed to remove soluble salts. 1n the latter casethe soluble salts can be removed by chill-setting and leaching or theemulsion can be coagulation washed.

The silver halide emulsions employed in the practice of the inventioncan be sensitized with chemical sensitizers, such as withreducing-agents; silver, selenium, or tellurium compounds; gold,platinum or palladium compounds; or combinations of these. Suitableprocedures are described, for example, in U.S. Pat. No. 1,623,499 ofShepardyissued Apr. 5, 1927; U.S. Pat. No. 2,399,083 of Waller et al.issued Apr. 23, 1946;

U.S. Pat. No. 3,297,447 of McVeigh issued'Jan. 10, 1967 and U.S. Pat.No. 3,297,446 of Dunn issued Jan.-

The silver halide emulsions and/orproc essing com-- positions employedin thepractice of the invention can contain speed increasing comoundssuch as polyalkylene glycols, cationic surfactants andthioethers orcomfor example, thiazolium salts; azaindenes, mercury salts asdescribed, for example, in U.S. Pat. No. 2,728,663

nates, carbodiimides, mixed function hardeners and of Allen et al.issued Dec. 27, 1955; urazoles; sulfocatechols; oximes described, forexample, in British Pat. No. 623,448; nitron; nitroindazoles;mercaptotetrazoles; polyvalent metal salts described, for example, inU.S. Pat. No. 2,839,405 of Jones issued June. 17, 1958; palladium,platinum and gold salts described, for

example, in U.S. Pat. No. 2,566,263 of'Trevelli et al.

polymeric hardeners such as oxidized polysaccharides such'as dialdehydestarch and oxyguargum and the like.

A photographic element and emulsions described in the practice of theinvention can contain various colloids alone or in combination asvehicles, binding agents and in various layers. Suitable hydrophilicmate-, rials include those naturally occurring substances such asproteins, for example, gelatin, gelatin derivatives, cellulosederivatives, polysaccharides such as dextran, gum arabic and the like;and synthetic polymeric substances such as water-soluble polyvinylcompounds like poly(vinylpyrrolidone), acrylamide polymers and the like.

The described photographic emulsion layers and other layers of thephotographic element employed in the practice of the invention can alsocontain, alone or in combination with hydrophilic, water-permeablecolloids, other synthetic polymeric compounds such as dispersed vinylcompounds, such as in latex form, and particularly those which increasethe dimensional stability of the photographic materials. Suitablesynthetic polymers include those described in U.S. Pat. No. 3,142,586 ofNottorf issued July 28, 1964; U.S. Pat.

No. 3,193,386 of White issued July 6, 1965; U.S. Pat.

No. 3,062,674 of l-louck et a1. issued Nov.-6, 1962; U.S. Pat. No.3,220,844 of Houck et al. issued Nov. 30, 1965; U.S. Pat. No. 3,287,289of Ream et al. issued Nov. 22, 1966-arld U.S. Pat. No.-.3,4 1 1,911 ofDykstra' issued Nov. 19, 1968. Particularly effective are thosewater-insoluble polymers of alkyl acrylates and methacrylates, acrylicacid, sulfoalkyl acrylates or m'ethacrylates, and those which havecrosslinking sites which facilitate hardening or curing as well as thosehaving recurring sulfo betaine units as described in Canadian Pat. No.774,054.

The photographicelments employed in the practice of the invention cancontain antistatic or conducting layers. Such layers can comprisesoluble salts such as chloride, nitrate and the like evaporated metallayers, ionic polymers such as those described in U.S. Pat. No.2,861,056 of Minsk issued Nov. 18, 1958 and U.S. Pat. No. 3,206,312 ofSterman et al. issued Sept 14, 1965 or insoluble organic salts such asthose described in U.S. Pat. No. 3,428,451 of Trevoy issued Feb. 18,1969.

The photographic emulsions and other layers of a photographic-elementemployed in the practice of the inventionand described herein can becoated on a wide variety of supports. Typical supports include cellulosenitrate film, cellulose ester film, poly(vinylacetal) film, polystyrenefilm, poly(ethylene terephthalate) film, polycarbonate film and relatedfilms or resinous materials as well as glass, paper, metal and the like.Typically a flexible support is employed, especially a paper supportwhich can be partially acetylated or coated with baryta and/or an alphaolefin polymer, particularly a polymer of an alpha olefin containing twoto carbon atoms such as polyethylene, poly-propylene, ethylene-butenecopolymers and the like.

The photographic elements employed in the practice of the invention cancontain plasticizers and lubricants such as polyalcohols, glycerin anddiols as described, for example, in U.S. Pat. No. 2,960,404 of Milton etal. issued Nov. 1, 1966; fatty acids or esters such as described in U.S.Pat. No. 2,588,765 of Robijns issued Mar. 11, 1952; and U.S. Pat. No.3,121,160 of Duane issued Feb. 11, 1964; and silicone resins such asthose described in British Pat. No. 955,061.

The photographic elements employed in the practice of the invention cancontain surfactants such as saponin, anionic compounds, such as alkylaryl sulfonates described, for example, in U.S. Pat. No. 2,600,831 ofBaldsiefen issued June 17, 1962 and amphoteric compounds such as thosedescribed in U.S. Pat. No. 3,133,816 of Ben-Ezra issued May 19, 1964.

The photographic elements employed in the practice of the invention cancontain matting agents such as startch, titanium dioxide, zinc oxide,silica, and polymeric beads including beads described, for example, inU.S. Pat. No. 2,992,101 of Jelley et al. issued July 11, 1961 and U.S.Pat. No. 2,701,245 of Lynn issued Feb. 1, 1955.

The described photographic elements employed in the practice of theinvention can also contain brightening agents including stilbene,triazine, oxazole, and/or coumarin brightening agents. Water-solublebrightenlide emulsions can conveniently be ortho-sensitized orpan-sensitized with spectral sensitizing dyes. For instance, theseemulsions can be spectrally sensitized by treating with a solution of asensitizing dye in an organic solvent or the dye can be added in theform of a dispersion such as described in French Pat. No. 1,482,774.Spectral sensitizing dyes useful in sensitizing such emulsions aredescribed, for example, in U.S. Pat. No. 2,526,632 of Brooker et al.issued Oct. 24, 1950; U.S. Pat. No. 2,503,776 of Sprague issued Apr. 11,1950; U.S. Pat. No. 2,493,748 of Brooker et a1. issued Jan. 10, 1950;and U.S. Pat. No. 3,384,486 of Taber et al. issued May 21, 1968.Spectral sensitizers which can be used include the cyanines,merocyanines, complex (trinuclear or tetranuclear) cyanines, complex(trinuclear or tetranuclear) merocyanines, holopolar cyanines, styryls,hemicyanines, such as enamine hemicyanines, oxonols and hemioxonols.Dyes of the cyanine classes can contain such basic groups as thethia'zolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles,selenazoles and imidazoles. Such groups can contain alkyl, alkylene,hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enaminesubstituents and can be fused to carbocyclic or heterocyclic ringsystems either unsubstituted or substituted with halogen, phenyl, alkyl,haloalkyl, cyano or alkoxy groups. The dyes can be symmetrical orunsymmetrical and can contain alkyl, phenyl, enamine or heterocyclicsubstituents on the methine or polymethine chain. The merocyanine dyescan contain the basic groups described as well as acid groups such asthiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones,barbituric acids, thiazolineones and malononitrile. These acid groupscan be substituted with alkyl, alkylene, phenyl, carboxyalkyl,sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups or heterocyclicgroups. Combinations of these dyes can be used if desired. In addition,supersensitizing addenda which do not absorb visible light can beincluded, such as ascorbic acid derivatives, azaindenes, cadmium saltsand organic sulfonic'acids as described in U.S. Pat. No. 2,933,390 ofMcFall et al. issued Apr. 19, 1960 and U.S. Pat. No. 2,937,089 of Joneset al. issued May 17, 1960.

The various layers including the photographic emulsion layer of thephotographic element employed in the practice of the invention cancontain light absorbing materials and filter dyes such as thosedescribed in U.S. Pat. No. 3,253,921 of Sawdey issued May 31, 1966; U.S.Pat. No. 2,274,782 of Gaspar issued Mar. 3, 1942; U.S. Pat. No.2,527,583 of Silberstein et al. issued Oct. 31, 1950 and U.S. Pat. No.2,956,879 of VanCampen issued Oct. 18. 1960. If desired, the dyes can bemordanted, for example, as described in U.S. Pat. No. 3,282,699 of Joneset al. issued Nov. 1, 1966.

The sensitizing dyes and other addenda used in thepracticeoftheinvention can be added from water solutions or suitableorganic solvent solutions can be used. The compounds can be added usingvarious procedures including those described in U.S. Pat. No. 2,912,343of Collins et al. issued Nov. 10, 1959; U.S. Pat. No. 3,342,605 ofMcCrossen et al. issued Sept. 19, 1967; U.S. Pat. No. 2,996,287 ofAudran issued Apr. 15', 1961 and U.S. Pat. No. 3,425,835 of Johnson etal. issued Feb. 4, 1969.

The following examples are included for a further understanding of theinvention.

EXAMPLE 1 This example illustrates use of the combination of thedescribed disulfones with a hydroxylamine silver halide developing agentand producing a positive image in a photographic chemical transfersystem.

A processing composition is prepared by mixing the following components.

Stock solution A (850 ml water, 213.2 g. potassium hydroxide with 0.16g.

4-thiazolidine2-thione) 45.0 ml Bis(methylsulfonyl)methane 1.65 gN-N-Diethylhydroxylamine 2.5 ml Hydroxyethylcellulose (Natrasol 25011sold by Hercules Powder Co., U.S.A.) 1.35 g

processing composition is spread between the photographic element andthe image receiver so as to have the image and receiver contact theprocessing composition simultaneously. After 30 seconds contact time at22C the photographic element with the processing layer is stripped awayfrom the image receiver. A positive image of good discrimination isobserved on the image receiver. The minimum reflection density of theimage on the image receiver is 0.08 and the maximum reflection densityof this image is 1.69.

EXAMPLE 2 This is a comparative example.

The procedure set out in Example 1 is repeated with the exception that1.08 grams of uracil is employed in place of bis(methylsulfonyl)methane. A transfer image is produced having a minimumreflection density of 0.10 and a maximum reflection density of 0.79.

EXAMPLE 3' This is a comparative example.

The procedure set out in Example 1 is repeated with the exception that2.38 grams of sodium thiosulfate pentahydrate is employed in place ofbis(methylsulfonyl)methane. A transfer image isproduced on the imagereceiver having a minimum reflection density of 0.30 and a maximumreflection density of .57.

EXAM LE 4 This is a comparative example.

The procedure set out in Example 1 is repreated with the exception that0.93 grams of potassium thiocyanate is employed in place of thebis(methylsulfonyl)methane. A transfer image is produced on the imagereceiver having a minimum reflection density of 0.10 and a maximumreflection density of 0.16.

EXAMPLE 5 This is a compative example.

The procedure set out in Example 1 is repeated with the exception that1.10 ml of an 80 percent by weight aqueous m'ercaptoacetic acid solutionis employed in place of the bis(methylsulfonyl)methane. A transfer imageis produced on the image receiver having a minimum reflection density of0.10 and a maximum reflection density of 0.10. This indicates nosatisfactory image transfer.

EXAMPLE 6 This is a comparative example;

The procedure set out in Example 1 is repeated with the exception that1.69 grams of cysteine hydrochloride monohydrate is employed in place ofthebis(methylsulfonyl)-methane. N0 satisfactory image transfer isobserved.

EXAMPLE 7 This is a comparative example.

The procedure set out in Example 1 is repeated with the exception that3.10 grams of hydroquinone is employed in place of theN,N-diethylhydroxylamine. An image transfer is obsreved on the imagereceiver having a minimum reflection density of 0.20 and a maximumreflection density of 1.10.

EXAMPLE 8' This is a comparative example.

The procedure set out in Example 1 is repeated with the exception that4.98 grams of D-(-)-araboascorbic acid is employed in place of theN,N-diethylhydroxylamine. A transfer image is produced on the imagereceiver having a minimum reflection density of 0.16 and a maximumreflection density of 0.8.6.

EXAMPLE 9 This examplesillustrates image stability of the image producedaccording to Example 1.

A print as produced according to Example 1 is subjected to the followingconditions:

Treatment Condition 22C., about 50% relative humidity, no light 38C.;about 90% relative humidity, 1800 foot-candles fluorescent illuminationIdentification Fresh Light incubated After 48 hours at the describedconditions, sensitometric-curves are plotted for the fresh and lightincubated samples. The following Table 1 indicates the stability ofprints producedaccording-to Example 1 as measured by the gain in speedat adensity of 0.20.

TABLE 1 Relative Speed at 0.2 Density (LogE) Light lncubated Speed Gain1 .04 0.04

Fresh Speed 1.00

This data indicates that very little less of image is produced uponincubation.

EXAMPLE 10 employing the different processing layer thicknesses,

The following is observed.

TABLE II Developer Layer Relative Speed Contrast Thickness Log E (at 0.2Density) Bar Gamma 0.0007 inch 1.00 1.67 0.0010 inch 1.00 1.68 0.97 1.58

0.0013 inch This illustrates that the photographic speed and contrastchange very little with processing layer thickness employing acombination according to the invention.

Results similar to those of Example 1 are obtained in each of thefollowing Examples 1 125 using the noted hydroxylamine silver halidedevelopingagents in place of N,N-diethylhydroxylamine.

7 EXAMPLE ll Hydroxylamine EXAMPLE 12 N-methylhydroxylamin'e 9 EXAMPLEl3 N-ethylhydroxylamine EXAMPLE l4 N-propylhydroxylamine EXAMPLE l5N-isopropylhydroxylamine EXAMPLE l6 N,N-dimethylhydroxylamine EXAMPLE l7I N-methyl-N-propylhydroxylamine EXAMPLE l8N-ethyl-N-propylhydroxylamine EXAMPLE l9 N,N-diisopropylhydroxylamineEXAMPLE 20 N,N-dimethylhydroxylamine EXAMPLE 21N-ethyl-N-hydroxyethylhydroxylamine Q EXAMPLE 22N-hydroxyethyl-N-carboxyethylhydroxylamine EXAMPLE 23N,N-di-(methoxyethyl) hydroxylamine EXAMPLE 24 N,N-di-(Z-ethoxyethyl)hydroxylamine EXAMPLE 25 N,N-di-( 2-methoxyethoxyethyl) hydroxylamineResults similar to those of Example 1 are obtained in each of thefollowing Examples using the noted 1,1-bissulfonyl alkane silver halidesolubilizing agent in place of bis(methylsulfonyl) methane.

EXAMPLE 26 l, l -Bis-(methylsulfonyl)ethane EXAMPLE 27l,l-Bis-(ethylsulfonyl)ethane v EXAMPLE 2 8 l,l -Bis-(methylsulfonyl)propane I EXAMPLE 29 l-e'thylsulfonyll -methyl sulfonylmethane EXAMPLE30 l-eth'ylsulfonyll -methylsulfonylethane EXAMPLE 31 l ,1-Bis-(beta-hydroxyethylsulfonyl)methane EXAMPLE 32 l, l-Bis-(carboxymethylsulfonyl)methane EXAMPLE 33 l, l -Bis-(beta-carboxyethylsulfonyl)methane EXAMPLE 34 The procedure set out inExample 1 is repeated with the exception that the processing compositiondescribed in Example 1 is replaced with the following processingcomposition:

Water 850.0 ml Potassium hydroxide 80.0 g Bis(methylsulfonyl)methane33.0 g p-Methylaminophenol sulfate 10.0

N J -diethyl hydroxylamine l7.0 ml 4-Thiaz0lidine-b 2-thione 0.2 gHydroxyethylcellulose (Natrasol 250B 27.0 3

sold by Hercules Powder Co., U.S.A.)

but it will be understood that variations and modifications can beeffected within the spirit and scope of the invention.

What is claimed is:

l. A photographic element comprising a support, photographic silverhalide, a l,l-bis-sulfonyl alkane silver halide solubilizing agent witha hydroxylamine silver halide developing agent. 2. Aphotographic elementas in claim 1 comprising a support, photographic silver halide,bis(methylsulwherein R and R each represent an alkyl group containingone to four carbon atoms and R represents hydrogen or an alkyl groupcontaining one to four carbon atoms, andsaid hydroxylamine silver halidedeveloping agent is a compound of the formula:'

wherein R, and R are each hydrogen, alkyl containing one to four carbonatoms, alkoxyalkyl containing three to six carbon atoms, oralkoxyalkoxyalkyl containing five to 10 carbon atoms.

5. The photographic diffusion transfer product of claim 3 wherein said1,1-bis-sulfonyl alkane is bis-(methylsulfonyl)methane and saidhydroxylamine silver halide developing agent isN,N-diethylhydroxylamine.

6. The photographic diffusion transfer product of claim 3 wherein saidl,l-bis-sulfonyl alkane and said hydroxylamine are present in saidprocessing composition.

7. The photographic diffusion transfer product of claim 3 wherein saiddiffusion transfer product} also comprises an auxiliary silver halidedeveloping agent. 8. The photographic diffusion transfer product ofclaim 3 wherein said diffusion transfer product also comprises anauxiliary silver halide developing agent which comprises an aminophenolsilver halide developing agent.

9. In a photographic diffusion transfer process comprising developing alatent image in a photographic diffusion transfer product comprising (a)a photographic element comprising photographic silver halide, (b) aprocessing composition comprising a silver halide solubilizing agent and(c) an image receiving layer, said product also comprising a silverhalide developing agent, and forming an imagewise distribution of asilver complex in said element by contacting undeveloped silver halidein said element with said silver halide solubilizing agent andtransferring at least part of the silver complex to said image receiverlayer, the improvement comprising employing a 1,1-bis-sulfonyl alkane assaid silver halide solubilizing agent and hydroxylamine as said silverhalide developing agent.

10. The photographic diffusion transfer process of claim 9 wherein saidl,l-bis-sulfonyl alkane is'acompound of the formula:

H8 wherein R and R each representan alkyl giofiiicdfi-i taining one tofour carbon atoms and R represents hydrogen or an alkyl group containingone to four carbon atoms, and said hydroxylamine silver halidedeveloping agent is a compound of the formula:

wherein R and R are each hydrogen, alkyl containing one to four carbonatoms, alkoxyalkyl containing three 1 agent.

I I I is QERTWMATE FQQRREQTTE I I -7?O. v Emma Ngvember 63 197iImnntofls) 90mm Gn Yenglwrich and 2m}! 5, Mcfiweeney I: is certitiafiqm@3250? eppeen'e m em ebesvve fidemaifia wfient ind that and Lemma esteemem hemby emrmew ma mew Mime:

time "A Phnmgraphic: fiezzrzp caeiif-imn ef'l l Bis-Sulfonyl Alkane enlHydrexylemine Shfiulfl reed ---Phocographic Compesiticm of l l fiieSulfenyl Alliance and Hydroxylaanii'le---'o Colman 1 line 55., agentezwuld rem} --e.gents--.

Column 5 line 1?; 12.3, shouifi read ---layer---. Line U5, photogrpehiflearl-maid reed ghutogrephic- Colman 6, line 3E3, "a" eheuld. be insertedafter "of" A. Line 65,. "l l bis sulfony" should read -----l,IL--ois:euliorzyl ea Column I8, line 53 after "ethoxy delete substituted 8Lines ERA-65, after "hydroquinone delete v "such as methoxy'hydrequinone m ethoxy hydroquinone,

Column 13 line 39 ,"compe'five" should read --e-comparative Line 62obsreved" sl'muld read ---observed---@ Column 16, line 8 iThiezolidine-b2-thione" should read r fhiazolidine-==2-ti:icmeo In theGleims:

Column 17, line 22, after and insert "a".

; Signed and sealed ihis let at October 1974,,

(SEAL) Attesc: v

.Q JY' Mo GIBSON JR, 7 C0 ML' ARSHALL DANN A; siihg Officer Commissionerof Patents

2. A photographic element as in claim 1 comprising a support,photographic silver halide, bis(methylsulfonyl)-methane andN,N-diethylhydroxylamine.
 3. In a photographic diffusion transferproduct comprising in combination (a) a photographic element comprisingphotographic silver halide, (b) a processing composition comprising asilver halide solubilizing agent and (c) an image-receiving layer, saidproduct containing a silver halide developing agent, the improvementcomprising a 1,1-bis-sulfonyl alkane as said silver halide solubilizingagent and a hydroxyl-amine silver halide developing agent as saiddeveloping agent.
 4. The photographic diffusion transfer product ofclaim 3 wherein said 1,1-bis-sulfonyl alkane is a compound of theformula:
 5. The photographic diffusion transfer product of claim 3wherein said 1,1-bis-sulfonyl alkane is bis-(methylsulfonyl)methane andsaid hydroxylamine silver halide developing agent isN,N-diethylhydroxylamine.
 6. The photographic diffusion transfer productof claim 3 wherein said 1,1-bis-sulfonyl alkane and said hydroxylamineare present in said processing composition.
 7. The photographicdiffusion transfer product of claim 3 wherein said diffusion transferproduct also comprises an auxiliary silver halide developing agent. 8.The photographic diffusion transfer product of claim 3 wherein saiddiffusion transfer product also comprises an auxiliary silver halidedeveloping agent which comprises an aminophenol silver halide developingagent.
 9. In a photographic diffusion transfer process comprisingdeveloping a latent image in a photographic diffusion transfer productcomprising (a) a photographic element comprising photographic silverhalide, (b) a processing composition comprising a silver halidesolubilizing agent and (c) an image receiving layer, said product alsocomprising a silver halide developing agent, and forming an imagewisedistribution of a silver complex in said element by contactingundeveloped silver halide in said element with said silver halidesolubilizing agent and transferring at least part of the silver complexto said image receiver layer, the improvement comprising employing a1,1-bis-sulfonyl alkane as said silver halide solubilizing agent andhydroxylamine as said silver halide developing agent.
 10. Thephotographic diffusion transfer process of claim 9 wherein said1,1-bis-sulfonyl alkane is a compound of the formula:
 11. Thephotographic diffusion transfer process of claim 9 wherein said1,1-bis-sulfonyl alkane is bis(methyl-sulfonyl)methaNe and saidhydroxylamine silver halide developing agent isN,N-diethylhydroxylamine.
 12. The photographic diffusion transferprocess of claim 9 wherein said processing composition also comprises anauxiliary silver halide developing agent. 13.The photographic diffusiontransfer process of claim 9 wherein said processing composition alsocomprises an auxiliary silver halide developing agent which comprises anaminophenol silver halide developing agent.